CN114122415A - Cathode structure catalyst layer of proton exchange membrane fuel cell and preparation method and application thereof - Google Patents
Cathode structure catalyst layer of proton exchange membrane fuel cell and preparation method and application thereof Download PDFInfo
- Publication number
- CN114122415A CN114122415A CN202111408415.9A CN202111408415A CN114122415A CN 114122415 A CN114122415 A CN 114122415A CN 202111408415 A CN202111408415 A CN 202111408415A CN 114122415 A CN114122415 A CN 114122415A
- Authority
- CN
- China
- Prior art keywords
- catalytic
- fuel cell
- catalyst layer
- mesoporous carbon
- cathode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
- H01M4/861—Porous electrodes with a gradient in the porosity
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8842—Coating using a catalyst salt precursor in solution followed by evaporation and reduction of the precursor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a cathode structure catalyst layer of a proton exchange membrane fuel cell, a preparation method and application thereof, wherein the method comprises the following steps: depositing and assembling mesoporous carbon sphere catalyst particles loaded with Pt on the surface of a substrate material by taking the mesoporous carbon sphere catalyst particles as basic catalytic units to obtain a sequential catalytic layer; the sequential structure of the imaginary catalyst layers is in an array laminated state, and specifically, catalytic particles are laid on a substrate material in an array state to form a catalyst layer or a plurality of catalyst layers are sequentially laminated; the catalyst layer is characterized by realizing two-stage multidimensional mass transfer channels, wherein the gaps among the Pt/MCS catalyst particles are first-stage mass transfer channels, and the mesopores on the surfaces of the Pt/MCS catalyst particles are second-stage mass transfer channels. The sequential catalyst layer is used for the cathode of the proton exchange membrane fuel cell, has higher mass transfer rate and lower ohmic polarization and concentration polarization, improves the catalytic efficiency of the catalyst, and can reduce the Pt loading capacity of the cathode so as to reduce the cost of the fuel cell.
Description
Technical Field
The invention belongs to the technical field of preparation of fuel cell cathode catalytic materials, and particularly relates to a cathode structure catalytic layer of a proton exchange membrane fuel cell, and a preparation method and application thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are energy conversion devices with zero emission, high efficiency and high power density, are widely regarded as the most promising sustainable green energy technology, and are also regarded as the core technology for building the "hydrogen energy society". At present, the reduction of the Pt loading capacity of the cathode and the realization of the high-performance and long-life operation of the PEMFCs are not only the key for determining whether the PEMFCs can be commercialized in a large scale, but also the key technical problem for developing the fuel cell industry.
The design and construction of the PEMFCs cathode catalyst layer under the micro-nano scale improve the multiphase transmission capacity of oxygen and water at a three-phase interface and improve the utilization rate of noble metal Pt, have become keys for further reducing the Pt loading capacity of the PEMFCs cathode catalyst layer and improving the performance of the catalyst layer, and are also the core of the conventional PEMFCs technology. Based on the above analysis of the prior art, there is a need to develop a new cathode structure catalyst layer of a proton exchange membrane fuel cell.
Disclosure of Invention
The invention aims to provide a cathode structure catalyst layer of a proton exchange membrane fuel cell, and a preparation method and application thereof, so as to solve one or more technical problems. The first aspect of the invention provides a sequential catalyst layer, which can improve the catalytic efficiency of a catalyst, reduce the Pt loading capacity of a cathode and further reduce the cost of a fuel cell; the second aspect of the invention provides a preparation method, which can ensure that Pt/MCS catalysis elements are orderly stacked and arranged to form a structured catalysis layer.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention relates to a cathode structure catalyst layer of a proton exchange membrane fuel cell, which comprises:
a substrate; depositing and assembling one or more mesoporous carbon sphere catalyst particle layers loaded with Pt on the surface of the substrate by using a vertical deposition self-assembly method;
wherein, the gaps among the Pt-loaded mesoporous carbon sphere catalyst particles form a primary mass transfer channel, and the surface mesopores of the Pt-loaded mesoporous carbon sphere catalyst particles form a secondary mass transfer channel.
A further improvement of the invention is that the substrate is a carbon cloth, a carbon paper or a Nafion membrane.
The further improvement of the invention is that in the mesoporous carbon sphere catalyst particles loaded with Pt, the mass ratio of Pt to the mesoporous carbon sphere catalyst particles loaded with Pt is 1-60%.
The invention discloses a preparation method of a cathode structure catalyst layer of a proton exchange membrane fuel cell, which comprises the following steps: and (3) depositing and assembling on the surface of the substrate by taking the Pt-loaded mesoporous carbon sphere catalyst particles as a catalysis basic unit to obtain the cathode structure catalyst layer of the proton exchange membrane fuel cell.
The further improvement of the invention is that the step of depositing and assembling the mesoporous carbon sphere catalyst particles loaded with Pt on the surface of the substrate by taking the mesoporous carbon sphere catalyst particles as the catalytic basic units specifically comprises the following steps:
and depositing and assembling on the surface of the substrate by using the vertical deposition self-assembly technology and taking the Pt-loaded mesoporous carbon sphere catalyst particles as a catalytic basic unit.
The further improvement of the invention is that the step of performing deposition assembly on the surface of the substrate by using the vertical deposition self-assembly technology and taking the mesoporous carbon sphere catalyst particles loaded with Pt as a catalytic basic unit specifically comprises the following steps:
dispersing Pt-loaded mesoporous carbon sphere catalyst particles in a water solution dissolved with Nafion and ethanol in a predetermined ratio to obtain a catalytic elementary dispersion liquid;
vertically inserting a substrate into the catalytic elementary dispersion liquid, standing for a preset time, after standing, adopting a vertical pulling or evaporating solution process to enable the liquid level of the catalytic elementary dispersion liquid and the substrate to move relatively, and gathering the Pt-loaded mesoporous carbon sphere catalyst particles under the action of capillary management and vertically depositing and self-assembling the Pt-loaded mesoporous carbon sphere catalyst particles on the substrate through ordered arrangement.
The further improvement of the invention is that the concentration of the Pt-loaded mesoporous carbon sphere catalyst particles in the catalytic element dispersion liquid is 0.1-100 mg/ml.
In a further improvement of the present invention, the vertically inserting the substrate into the catalytic cell dispersion liquid for a predetermined time further comprises: and keeping the dispersion liquid at a constant temperature in the standing process, wherein the value range of the constant temperature is 1-80 ℃.
The further improvement of the invention is that when the vertical deposition self-assembly is carried out, the size and the arrangement mode of the catalytic elements are adjusted and controlled to adjust the gaps among the particles, thereby realizing the size adjustment of the primary mass transfer channel; when the vertical deposition self-assembly is carried out, the mesopores in the structural catalyst layer are adjusted by adjusting and controlling the pore size distribution of the surface mesopores of the catalytic elements, so that the distribution adjustment of a secondary mass transfer channel is realized; when the vertical deposition self-assembly is carried out, the surface doping state, the surface defects and the hydrophobicity of a mass transfer channel in the sequential catalyst layer are adjusted by adjusting and controlling the surface doping state, the surface defects and the hydrophobicity-philic property of the catalytic element; when the vertical deposition self-assembly is carried out, the structure state of the structure catalysis layer is adjusted by adjusting and controlling the self-assembly time.
The cathode structure catalyst layer of the proton exchange membrane fuel cell is used as the cathode of the proton exchange membrane fuel cell.
Compared with the prior art, the invention has the following beneficial effects:
the sequential catalyst layer provided by the first aspect of the invention is used for a proton exchange membrane fuel cell cathode, has higher mass transfer rate, lower ohmic polarization and concentration polarization, improves the catalyst catalysis efficiency, and can reduce the Pt loading capacity of the cathode so as to reduce the cost of the fuel cell. Specifically, mesoporous carbon sphere catalyst particles loaded with Pt are used as a catalytic basic unit to be deposited and assembled on the surface of a substrate material to obtain a cathode structure catalytic layer of the proton exchange membrane fuel cell; the catalyst layer sequential structure is in an array laminated state, and specifically catalytic particles are spread on a substrate material in an array state to form a catalyst layer or multiple catalyst layers are sequentially laminated; the catalyst layer is characterized in that two-stage multidimensional mass transfer channels can be realized, specifically, the gaps among the Pt/MCS catalyst particles are first-stage mass transfer channels, the mesoporous surfaces of the Pt/MCS catalyst particles are second-stage mass transfer channels, and the two-stage channels can realize multidimensional mass transfer.
The preparation method provided by the second aspect of the invention can complete the synthesis of the cathode structure catalyst layer of the proton exchange membrane fuel cell, and can ensure that Pt/MCS catalysis elements are orderly stacked and arranged to form the structure catalyst layer.
The preparation method provided by the invention discloses a technical scheme for vertically depositing Pt/MCS catalysis elements on a carbon fiber product or a Nafion membrane, and is a convenient and controllable preparation method of a cathode structure catalysis layer of a proton exchange membrane fuel cell; the preparation method of the invention not only can complete the synthesis of the cathode structure catalyst layer of the proton exchange membrane fuel cell, but also can ensure that the Pt/MCS catalyst layer can have a step distribution mass transfer channel.
Further specifically, the number and the degree of the order of the catalyst layers can be regulated and controlled by controlling the concentration of the colloidal dispersion, the polarity of the solution, the self-assembly temperature and the self-assembly time; by controlling the size, arrangement mode, surface mesoporous aperture distribution, surface doping state, surface defect and hydrophilic and hydrophobic properties of Pt/MCS catalytic elements, the size of a particle gap macropore (a primary mass transfer channel) can be adjusted, and the mesoporous distribution (a secondary mass transfer channel) in a catalytic layer, the surface doping state, the surface defect and the hydrophilic and hydrophobic properties of the mass transfer channel can be adjusted. The mass transfer rate in the catalyst layer can be improved and the catalytic efficiency can be improved through the regulation.
In the application of the invention, Pt/MCS particles are deposited and assembled on the surface of a substrate material by utilizing a vertical deposition self-assembly technology to obtain a cathode structure catalyst layer of the proton exchange membrane fuel cell, and the substrate and the catalyst layer deposited and attached on the substrate jointly form a composite electrode as a cell cathode.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art are briefly introduced below; it is obvious that the drawings in the following description are some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a schematic diagram illustrating the principle of the product according to the embodiment of the present invention
FIG. 2 is a schematic diagram of the preparation of a Pt/MCS catalytic element according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of a cathode structure catalyst layer vertical deposition self-assembly process according to an embodiment of the present invention;
FIG. 4 is a Scanning Electron Microscope (SEM) of Pt/MCS single-layer elementary sequence catalytic layer prepared by the embodiment of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
referring to fig. 1, a cathode structure catalyst layer of a proton exchange membrane fuel cell according to an embodiment of the present invention includes:
a substrate; depositing and assembling one or more mesoporous carbon sphere catalyst particle layers loaded with Pt on the surface of the substrate by using a vertical deposition self-assembly method;
wherein, the gaps among the Pt-loaded mesoporous carbon sphere catalyst particles form a primary mass transfer channel, and the surface mesopores of the Pt-loaded mesoporous carbon sphere catalyst particles form a secondary mass transfer channel.
The space structure of the catalyst layer in the embodiment of the invention is structured in an array lamination way, and specifically comprises the following steps: the Pt/MCS catalytic particles in each layer are sequentially contacted to form an array, and each Pt/MCS catalytic particle falls on the gap of another row of catalytic particles between rows or columns, so as to be arranged to form a single-layer catalytic layer; on the basis, each layer of Pt/MCS catalytic particles in the back layer has the same arrangement mode and are sequentially added in a stacking mode, but each Pt/MCS catalytic particle falls on the gap of another layer of catalytic particles between the layers, and the Pt/MCS catalytic particles are arranged into the array-stacked catalytic layers in sequence; the catalyst layer is characterized in that two-stage multidimensional mass transfer channels can be realized, specifically, the gaps among the Pt/MCS catalyst particles are first-stage mass transfer channels, the mesoporous surfaces of the Pt/MCS catalyst particles are second-stage mass transfer channels, and the two-stage channels can realize multidimensional mass transfer.
The preparation method of the cathode sequential catalyst layer of the proton exchange membrane fuel cell comprises the following steps:
and (2) depositing and assembling Mesoporous Carbon sphere catalyst (Pt/Mesoporous Carbon Spheres, Pt/MCS) particles loaded with Pt on the surface of a substrate material by taking the Pt/Mesoporous Carbon sphere catalyst as a catalytic basic unit to obtain the cathode structure catalytic layer of the proton exchange membrane fuel cell.
The preparation method provided by the embodiment of the invention can not only complete the synthesis of the cathode structure catalyst layer of the proton exchange membrane fuel cell, but also ensure that the Pt/MCS catalyst layer can have a gradient distribution mass transfer channel.
In another preferred embodiment of the present invention, the step of obtaining the cathode sequential catalyst layer of the pem fuel cell by depositing and assembling Pt/MCS particles as a catalytic basic unit on the surface of the substrate material by using a vertical deposition self-assembly technique specifically includes:
dispersing Pt/MCS catalysis element particles in a water solution dissolved with Nafion and ethanol in a certain proportion by utilizing ultrasound to obtain a catalysis element dispersion liquid;
the method comprises the steps of vertically inserting a substrate material into a catalytic element dispersion liquid, dipping for a preset time, enabling the liquid level of the dispersion liquid and the substrate material to move relatively by adopting a vertical solution pulling or evaporating process, enabling Pt/MCS catalytic elements to be gathered under the action of capillary management and vertically deposited on the substrate material through ordered arrangement (illustratively, a very thin liquid film can be formed in a meniscus region at a three-phase interface of the dispersion liquid, the substrate and air at the moment, enabling the Pt/MCS catalytic elements to be gathered together under the action of capillary management when the thickness of the liquid film is reduced to be below the grain size of the Pt/MCS catalytic elements, obtaining a single-layer or multi-layer sequential catalytic layer through ordered stacking arrangement), and obtaining the single-layer or multi-layer sequential catalytic layer through ordered stacking arrangement.
In the embodiment of the invention, the substrate material is carbon cloth, carbon paper or a Nafion film. The Mesoporous Carbon Spheres (MCS) with different particle sizes and Mesoporous surfaces are prepared by a copolycondensation method. The Pt-loaded Mesoporous Carbon sphere catalyst (Pt/MeOPOROUS CARBON Spheres, Pt/MCS) particles are loaded in a microwave-assisted polyol reduction method, a polyol solution heating reduction method, a hydrogen reduction method, sodium borohydride/potassium borohydride normal-temperature reduction method, a dipping reduction method, an electrochemical deposition method, a sol-gel method and a chemical evaporation deposition method (CVD).
In the embodiment of the invention, after the Pt/MCS catalytic element is deposited on the carbon fiber product or the Nafion film as the substrate, the method further comprises the following steps: and drying to obtain the final cathode structure catalyst layer of the proton exchange membrane fuel cell.
The embodiment of the invention is exemplarily and optionally used, and before vertical deposition self-assembly, dispersing liquid base liquids with different proportions are obtained by changing the ratio of Nafion/ethanol/water, specifically, the volume proportions of Nafion/ethanol/water are respectively 5% -30% Nafion/5% -30% ethanol/40% -90% water. The platinum loading capacity of the Pt/MCS catalytic element is changed, and the specific mass ratio of the Pt to the Pt/MCS catalytic element is 1-60%. The amount of Pt/MCS catalytic elements is changed to obtain dispersion liquid with different concentrations so as to regulate and control the number of layers of the catalytic elements, and specifically, the concentration of the dispersion liquid is 0.1 mg/ml-100 mg/ml. When vertical deposition self-assembly is carried out, the catalyst sequence degree is adjusted by adjusting and controlling the self-assembly temperature and the solution polarity, specifically, a constant temperature is supplied to the dispersion liquid through an oil bath pot, and the temperature range of the constant temperature is 1-80 ℃.
The embodiment of the invention exemplifies that when the vertical deposition self-assembly is carried out, the residence time of the substrate material in the Pt/MCS catalytic element dispersion liquid can be 0.01-24 hours.
In conclusion, when the vertical deposition self-assembly is carried out, the size of the large pores in the gaps of the particles is adjusted by adjusting and controlling the size and the arrangement mode of the Pt/MCS catalytic elements; adjusting the mesopore distribution in the elementary sequence structure catalyst layer by adjusting and controlling the surface mesopore size distribution of the Pt/MCS catalyst elementary; the surface doping state, the surface defects and the hydrophilic and hydrophobic properties of a mass transfer channel in the catalyst layer of the element structure are adjusted by adjusting and controlling the surface doping state, the surface defects and the hydrophilic and hydrophobic properties of the Pt/MCS catalytic element; the self-assembly time is adjusted and controlled, namely the speed of the substrate material vertically pulling or evaporating the solution from the Pt/MCS catalysis element dispersion liquid is adjusted and controlled, so that the relative movement speed of the substrate material relative to the liquid level of the dispersion liquid or the liquid level of the dispersion liquid relative to the substrate material is adjusted and controlled, and the sequential state of the catalysis layer is adjusted; illustratively, the substrate is optionally pulled upwards or the liquid level moving speed during evaporation is 0.1 cm/s-5 cm/s.
Example 1
The preparation method of the cathode sequential catalyst layer of the proton exchange membrane fuel cell comprises the following steps:
step 1, preparing a Pt-loaded mesoporous carbon sphere (Pt/MCS) catalyst by using a microwave-assisted reduction method, which is a method for quickly and uniformly preparing a platinum catalyst by microwave assistance.
Step 2, taking the Pt/MCS catalyst as a catalytic element, and dispersing Pt/MCS catalytic element particles in a certain proportion of Nafion/ethanol/water solution by using ultrasound to obtain a catalytic element dispersion liquid;
and 3, vertically inserting the carbon fiber product or the Nafion film serving as a deposition substrate into the Pt/MCS catalytic element dispersion liquid for a certain time, and then vertically pulling the substrate material out of the liquid level of the dispersion liquid at a certain speed along the original path, or evaporating the dispersion liquid at a certain speed to lower the liquid level while fixing the substrate material in the dispersion liquid at a constant position.
And 4, pulling the substrate material away from the dispersion liquid or evaporating the dispersion liquid to lower the liquid level, wherein the substrate material forms a very thin liquid film in a meniscus region at the liquid level of the dispersion liquid (namely at the three-phase interface of the dispersion liquid, the substrate material and the air), and when the thickness of the liquid film is reduced to be below the particle size of the Pt/MCS catalytic elements, the Pt/MCS catalytic elements are gathered together under the action of capillary management, and the single-layer or multi-layer structure catalytic layer is obtained through ordered stacking and arrangement.
And 5, drying the single-layer or multi-layer sequential catalyst layer which is formed by vertical deposition and self-assembly and is arranged in an orderly stacked manner to obtain the cathode sequential catalyst layer of the proton exchange membrane fuel cell.
Wherein, the platinum loading of the Pt/MCS catalytic element is that the mass ratio of Pt to Pt/MCS catalytic element is 20-40%; the proportion of Nafion/ethanol/water in the dispersion liquid is respectively 5-30% of Nafion/5-30% of ethanol/40-90% of water; the concentration of the Pt/MCS catalytic element is 5-50 mg/20 ml-500 mg/5-50 ml; the vertical deposition self-assembly temperature is that the dispersion liquid is supplied with a constant temperature through an oil bath pot, and the temperature interval is 1-80 ℃; the residence time of the substrate material in the Pt/MCS catalysis element dispersion liquid is specifically increased to 0.01-24 hours; the vertical deposition self-assembly speed is mainly adjusted and controlled by adjusting and controlling the self-assembly time, namely adjusting and controlling the vertical pulling speed of the base material from the Pt/MCS catalytic element dispersion liquid or the speed of evaporating the solution, and specifically the relative movement speed of the liquid level of the dispersion liquid and the base material is 0.1 cm/s-5 cm/s; the number and the degree of the order structure of the catalyst layers are regulated and controlled by controlling the concentration of the colloidal dispersion liquid, the polarity of the solution, the self-assembly temperature and the self-assembly time; by controlling the size, arrangement mode, surface mesoporous aperture distribution, surface doping state, surface defect and hydrophilic and hydrophobic properties of Pt/MCS catalytic elements, the size of a particle gap macropore (a primary mass transfer channel) can be adjusted, and the mesoporous distribution (a secondary mass transfer channel) in a catalytic layer, the surface doping state, the surface defect and the hydrophilic and hydrophobic properties of the mass transfer channel can be adjusted. The mass transfer rate in the catalyst layer can be improved and the catalytic efficiency can be improved through the regulation.
Example 2
Referring to fig. 2 to fig. 4, a method for preparing a cathode structure catalyst layer of a proton exchange membrane fuel cell based on vertical deposition self-assembly according to an embodiment of the present invention includes: as shown in FIG. 2, Mesoporous Carbon Spheres (MCS) are obtained by pyrolysis at 800 ℃ and etching with 1mol/L NaOH solution for 12h by adopting a copolycondensation method, and then the MCS is treated by adopting a microwave-assisted polyol reduction method to load Pt. The platinum source was 0.05mol/L H2PtCl6 in water, and the platinum loading was 30% by mass of Pt to Pt/MCS in terms of catalytic elements. 200mg of the obtained Pt/MCS catalytic element is taken, and Pt/MCS catalytic element particles are dispersed in 50ml of Nafion/ethanol/water solution with the proportion of 5%/15%/80% for 30min by ultrasonic treatment to form stable dispersion liquid. The dispersion was then left at room temperature, and the carbon paper was vertically inserted into the dispersion, left to stand and retained for 30 seconds. After the detention is finished, the carbon paper is vertically pulled upwards along the original path at the speed of 0.5cm/s by adopting a vertical deposition self-assembly method as shown in figure 3, and the catalytic elements are orderly stacked and arranged on the carbon paper along with the orientation and constant-speed movement of the carbon paper under the capillary management at the three-phase interface of the dispersion liquid, the surface of the carbon paper and the air, wherein the dispersion liquid is in contact with the liquid surface of the dispersion liquid. And (3) drying the carbon paper at 80 ℃ after the carbon paper completely leaves the liquid level of the dispersion liquid to obtain the Pt/MCS ordered catalyst layer.
As shown in FIG. 4, FIG. 4 is a Scanning Electron Microscope (SEM) of Pt/MCS single-layer elementary sequence catalyst layer prepared by the embodiment of the present invention. It can be seen that the Pt/MCS catalysis elements are orderly arranged on a two-dimensional plane, and a first-stage mass transfer channel (Pt/MCS sphere gap) and a second-stage mass transfer channel (Pt/MCS surface mesoporous) in the orderly catalysis layer are clearly visible.
The embodiment of the invention provides a preparation method of a cathode sequential catalyst layer of a proton exchange membrane fuel cell based on vertical deposition self-assembly, belonging to the technical field of preparation of cathode catalytic materials of fuel cells. The method takes Pt-loaded mesoporous carbon spheres (Pt/MCS) as catalytic elements; dispersing the catalytic element in Nafion/ethanol/water solution in a certain proportion by using ultrasonic to form stable dispersion liquid; taking a carbon fiber product or a Nafion film as a substrate, and orderly accumulating catalytic elements on the substrate in a dispersion liquid by a vertical deposition self-assembly method; finally, the Pt/MCS ordered catalyst layer is obtained by drying. The preparation method of the cathode structure catalyst layer of the proton exchange membrane fuel cell is simple to operate, low in cost, convenient and fast, and adjustable, can complete synthesis of the cathode catalyst layer of the proton exchange membrane fuel cell, and can ensure that the Pt/MCS catalyst layer can have a step distribution mass transfer channel, improve the mass transfer rate in the catalyst layer and improve the catalytic efficiency. The process is integrated and rapid, and the prepared cathode structure catalyst layer of the fuel cell has a multi-dimensional grading mass transfer channel and has potential industrial value.
Example 3
The embodiment of the invention discloses a preparation method of a cathode sequential catalyst layer of a proton exchange membrane fuel cell based on vertical deposition self-assembly, which is only different from the embodiment 2 in that: the pyrolysis temperature is changed from 800 ℃ to 900 ℃ when preparing the Mesoporous Carbon Spheres (MCS).
Example 4
The embodiment of the invention discloses a preparation method of a cathode sequential catalyst layer of a proton exchange membrane fuel cell based on vertical deposition self-assembly, which is only different from the embodiment 2 in that: when the Mesoporous Carbon Spheres (MCS) are prepared, the etching process is changed from etching with 1mol/L NaOH solution for 12 hours to etching with 2mol/L NaOH solution for 24 hours.
Example 5
The embodiment of the invention discloses a preparation method of a cathode sequential catalyst layer of a proton exchange membrane fuel cell based on vertical deposition self-assembly, which is only different from the embodiment 4 in that: changing a method for loading platinum, and processing MCS by adopting a chemical evaporation deposition method to load Pt, wherein the platinum loading amount is that the mass ratio of Pt to Pt/MCS is 35%.
Example 6
The embodiment of the invention discloses a preparation method of a cathode sequential catalyst layer of a proton exchange membrane fuel cell based on vertical deposition self-assembly, which is only different from the embodiment 4 in that: changing the proportion of the reagents of the dispersion base liquid, and dispersing Pt/MCS catalytic elementary particles in 50ml of Nafion/ethanol/water solution with the proportion of 10%/10%/80% for 30min by ultrasonic treatment.
Example 7
The embodiment of the invention discloses a preparation method of a cathode sequential catalyst layer of a proton exchange membrane fuel cell based on vertical deposition self-assembly, which is only different from the embodiment 4 in that: when the vertical deposition self-assembly is carried out, the vertical deposition self-assembly temperature is changed, the dispersion liquid is placed in an oil bath kettle under the constant temperature condition of 80 ℃, the carbon paper is vertically inserted into the dispersion liquid, and the carbon paper is kept standing for 1 hour.
Example 8
The embodiment of the invention discloses a preparation method of a cathode sequential catalyst layer of a proton exchange membrane fuel cell based on vertical deposition self-assembly, which is only different from the embodiment 4 in that: before the vertical deposition self-assembly, the concentration of the catalytic element dispersion liquid is changed, namely the amount of the catalytic element is changed, and 300mg of Pt/MCS catalytic element is taken to be dispersed in 50ml of Nafion/ethanol/water solution with the proportion of 5%/15%/80%.
Example 9
The embodiment of the invention discloses a preparation method of a cathode sequential catalyst layer of a proton exchange membrane fuel cell based on vertical deposition self-assembly, which is only different from the embodiment 4 in that: the residence time of the carbon paper in the dispersion was changed, and the carbon paper was vertically inserted into the dispersion, left to stand and retained for 12 hours.
Example 10
The embodiment of the invention discloses a preparation method of a cathode sequential catalyst layer of a proton exchange membrane fuel cell based on vertical deposition self-assembly, which is only different from the embodiment 4 in that: when the vertical deposition self-assembly is carried out, the vertical pulling speed of the carbon paper is changed, and the carbon paper is pulled vertically upwards along the original path at the speed of 0.1 cm/s.
Example 11
The embodiment of the invention discloses a preparation method of a cathode sequential catalyst layer of a proton exchange membrane fuel cell based on vertical deposition self-assembly, which is only different from the embodiment 4 in that: the carbon paper was inserted vertically into the dispersion, left to stand and retained for 24 hours. After the detention is finished, the carbon paper still keeps standing, the dispersion liquid starts to evaporate, the liquid level of the dispersion liquid is lowered at the speed of 0.2cm/s, and at the moment, the dispersion liquid in contact with the liquid level of the dispersion liquid, the surface of the carbon paper and an air three-phase interface move along with the liquid level of the dispersion liquid at a fixed speed under the action of capillary management to be orderly stacked and arranged on the carbon paper. And (3) drying the carbon paper at 80 ℃ after the carbon paper is completely separated from the liquid level of the dispersion liquid to obtain the Pt/MCS ordered catalyst layer.
Example 12
The embodiment of the invention discloses a preparation method of a cathode sequential catalyst layer of a proton exchange membrane fuel cell based on vertical deposition self-assembly, which is only different from the embodiment 4 in that: in the vertical deposition self-assembly process, a Nafion film is vertically inserted into the Pt/MCS catalytic element dispersion liquid as a substrate.
Example 13
The embodiment of the invention discloses a preparation method of a cathode sequential catalyst layer of a proton exchange membrane fuel cell based on vertical deposition self-assembly, which is only different from the embodiment 4 in that: changing a method for loading platinum, and adopting a polyol solution heating reduction method to process MCS to load Pt, wherein the platinum loading amount is that the mass ratio of Pt to Pt/MCS is 25%.
Example 14
The embodiment of the invention discloses a preparation method of a cathode sequential catalyst layer of a proton exchange membrane fuel cell based on vertical deposition self-assembly, which is only different from the embodiment 4 in that: changing a method for loading platinum, and adopting a dipping reduction method to process the MCS to load Pt, wherein the platinum loading amount is that the mass ratio of Pt to Pt/MCS is 25%.
Example 15
The embodiment of the invention discloses a preparation method of a cathode sequential catalyst layer of a proton exchange membrane fuel cell based on vertical deposition self-assembly, which is only different from the embodiment 4 in that: changing a method for loading platinum, and processing MCS by adopting an electrochemical deposition method to load Pt, wherein the platinum loading amount is that the mass ratio of Pt to Pt/MCS is 25%.
Example 16
The embodiment of the invention discloses a preparation method of a cathode sequential catalyst layer of a proton exchange membrane fuel cell based on vertical deposition self-assembly, which is only different from the embodiment 4 in that: changing a method for loading platinum, and processing MCS by adopting a sol-gel method to load Pt, wherein the platinum loading amount is that the mass ratio of Pt to Pt/MCS is 25%.
Example 17
The preparation method of the cathode sequential catalyst layer of the proton exchange membrane fuel cell comprises the following steps:
depositing and assembling mesoporous carbon sphere catalyst particles loaded with Pt on the surface of a substrate by using a vertical deposition self-assembly technology as a catalysis basic unit to obtain a cathode structure catalyst layer of the proton exchange membrane fuel cell;
the method comprises the following steps of depositing and assembling on the surface of a substrate by taking Pt-loaded mesoporous carbon sphere catalyst particles as catalytic basic units: dispersing Pt-loaded mesoporous carbon sphere catalyst particles in a water solution dissolved with Nafion and ethanol in a predetermined ratio to obtain a catalytic elementary dispersion liquid; vertically inserting a substrate into the catalytic elementary dispersion liquid, standing for a preset time, after standing, adopting a vertical pulling or evaporating solution process to enable the liquid level of the catalytic elementary dispersion liquid and the substrate to move relatively, and gathering the Pt-loaded mesoporous carbon sphere catalyst particles under the action of capillary management and vertically depositing and self-assembling the Pt-loaded mesoporous carbon sphere catalyst particles on the substrate through ordered arrangement;
the concentration of the Pt-loaded mesoporous carbon sphere catalyst particles is 0.1 mg/ml; keeping the dispersion liquid at a constant temperature in the standing process, wherein the value range of the constant temperature is 1 ℃; in the mesoporous carbon sphere catalyst particles loaded with Pt, the mass ratio of Pt to the mesoporous carbon sphere catalyst particles loaded with Pt is 1%.
Example 18
The preparation method of the cathode sequential catalyst layer of the proton exchange membrane fuel cell in the embodiment of the invention is different from the preparation method in the embodiment 17 only in that the concentration of the Pt-loaded mesoporous carbon sphere catalyst particles is 50 mg/ml; keeping the dispersion liquid at a constant temperature in the standing process, wherein the value range of the constant temperature is 40 ℃; in the mesoporous carbon sphere catalyst particles loaded with Pt, the mass ratio of Pt to the mesoporous carbon sphere catalyst particles loaded with Pt is 30%.
Example 19
The preparation method of the cathode sequential catalyst layer of the proton exchange membrane fuel cell in the embodiment of the invention is different from the preparation method in the embodiment 17 only in that the concentration of the Pt-loaded mesoporous carbon sphere catalyst particles is 100 mg/ml; keeping the dispersion liquid at a constant temperature in the standing process, wherein the value range of the constant temperature is 80 ℃; in the mesoporous carbon sphere catalyst particles loaded with Pt, the mass ratio of Pt to the mesoporous carbon sphere catalyst particles loaded with Pt is 60%.
In the embodiment of the invention, the relation between the mass transfer performance and the ordering degree of the sequential catalyst layer can be researched by utilizing numerical simulation; simulating Pt-loaded mesoporous carbon sphere catalyst particles into regular spheres and respectively establishing two models, wherein the spatial structure of the first model is set as that two spheres with different radiuses are arranged in sequence at intervals, specifically, small spheres are inserted into gaps of ordered large spheres, and the spatial structure of the second model is a more regular ordered large sphere model, specifically, only the large spheres are arranged in a sequence array in space; the two models respectively compare the oxygen and water mass transfer characteristics at 60 ℃ and 1 atmospheric pressure, and the result shows that the catalytic layer model II with the two-stage mass transfer channel having a higher ordered structure shows smaller mass transfer pressure drop and has higher mass transfer efficiency. It can be seen from the simulation that the higher the degree of the catalytic layer structure, the more advantageous the mass transfer process when the electrochemical reaction on the cathode proceeds.
In summary, the embodiment of the invention discloses a preparation method and application of a cathode structure catalyst layer of a proton exchange membrane fuel cell, wherein the preparation method specifically comprises the following steps: taking a Pt-loaded mesoporous carbon sphere (Pt/MCS) catalyst as a catalytic element, and dispersing Pt/MCS catalytic element particles in a certain proportion of Nafion/ethanol/water solution by using ultrasound to obtain a catalytic element dispersion liquid; and (3) taking the carbon fiber product as a substrate, and obtaining a single-layer or multi-layer structure catalyst layer by using ordered stacking arrangement formed by a vertical deposition self-assembly technology to obtain the cathode structure catalyst layer of the proton exchange membrane fuel cell. The invention can synthesize the catalyst layer which is structured and provided with the mass transfer channels distributed in a gradient way, thereby improving the mass transfer rate and the catalytic efficiency in the catalytic process.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (10)
1. A cathode-sequence catalyst layer of a proton exchange membrane fuel cell, comprising:
a substrate; depositing and assembling one or more mesoporous carbon sphere catalyst particle layers loaded with Pt on the surface of the substrate by using a vertical deposition self-assembly method;
wherein, the gaps among the Pt-loaded mesoporous carbon sphere catalyst particles form a primary mass transfer channel, and the surface mesopores of the Pt-loaded mesoporous carbon sphere catalyst particles form a secondary mass transfer channel.
2. The cathode catalyst layer of proton exchange membrane fuel cell according to claim 1, wherein the substrate is carbon cloth, carbon paper or Nafion membrane.
3. The cathode sequential catalyst layer of a proton exchange membrane fuel cell according to claim 1, wherein the mass ratio of Pt to the Pt-loaded mesoporous carbon sphere catalyst particles is 1% to 60%.
4. A preparation method of a cathode structure catalyst layer of a proton exchange membrane fuel cell is characterized by comprising the following steps: and (3) depositing and assembling on the surface of the substrate by taking the Pt-loaded mesoporous carbon sphere catalyst particles as a catalysis basic unit to obtain the cathode structure catalyst layer of the proton exchange membrane fuel cell.
5. The preparation method according to claim 4, wherein the step of depositing and assembling the Pt-loaded mesoporous carbon sphere catalyst particles on the surface of the substrate by taking the Pt-loaded mesoporous carbon sphere catalyst particles as the catalytic basic units comprises the following specific steps:
and depositing and assembling on the surface of the substrate by using the vertical deposition self-assembly technology and taking the Pt-loaded mesoporous carbon sphere catalyst particles as a catalytic basic unit.
6. The preparation method according to claim 5, wherein the step of performing deposition assembly on the surface of the substrate by using the Pt-loaded mesoporous carbon sphere catalyst particles as catalytic basic units by using a vertical deposition self-assembly technology specifically comprises:
dispersing Pt-loaded mesoporous carbon sphere catalyst particles in a water solution dissolved with Nafion and ethanol in a predetermined ratio to obtain a catalytic elementary dispersion liquid;
vertically inserting a substrate into the catalytic elementary dispersion liquid, standing for a preset time, after standing, adopting a vertical pulling or evaporating solution process to enable the liquid level of the catalytic elementary dispersion liquid and the substrate to move relatively, and gathering the Pt-loaded mesoporous carbon sphere catalyst particles under the action of capillary management and vertically depositing and self-assembling the Pt-loaded mesoporous carbon sphere catalyst particles on the substrate through ordered arrangement.
7. The production method according to claim 6, wherein the concentration of the Pt-loaded mesoporous carbon sphere catalyst particles in the catalyst element dispersion is 0.1mg/ml to 100 mg/ml.
8. The method of claim 6, wherein the vertically inserting a substrate into the catalytic cell dispersion for a predetermined time further comprises:
and keeping the dispersion liquid at a constant temperature in the standing process, wherein the value range of the constant temperature is 1-80 ℃.
9. The production method according to claim 5,
when the vertical deposition self-assembly is carried out, the size and the arrangement mode of the catalytic elements are adjusted and controlled to adjust the gaps among the particles, so that the size adjustment of a primary mass transfer channel is realized;
when the vertical deposition self-assembly is carried out, the mesopores in the structural catalyst layer are adjusted by adjusting and controlling the pore size distribution of the surface mesopores of the catalytic elements, so that the distribution adjustment of a secondary mass transfer channel is realized;
when the vertical deposition self-assembly is carried out, the surface doping state, the surface defects and the hydrophobicity of a mass transfer channel in the sequential catalyst layer are adjusted by adjusting and controlling the surface doping state, the surface defects and the hydrophobicity-philic property of the catalytic element;
when the vertical deposition self-assembly is carried out, the structure state of the structure catalysis layer is adjusted by adjusting and controlling the self-assembly time.
10. Use of the cathode catalyst layer of the pem fuel cell of claim 1 as a pem fuel cell cathode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111408415.9A CN114122415A (en) | 2021-11-24 | 2021-11-24 | Cathode structure catalyst layer of proton exchange membrane fuel cell and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111408415.9A CN114122415A (en) | 2021-11-24 | 2021-11-24 | Cathode structure catalyst layer of proton exchange membrane fuel cell and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114122415A true CN114122415A (en) | 2022-03-01 |
Family
ID=80372441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111408415.9A Pending CN114122415A (en) | 2021-11-24 | 2021-11-24 | Cathode structure catalyst layer of proton exchange membrane fuel cell and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114122415A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101000967A (en) * | 2007-01-11 | 2007-07-18 | 上海交通大学 | Membrane electrode of protone exchange membrane fuel cell and preparation method thereof |
| CN101109070A (en) * | 2007-07-02 | 2008-01-23 | 南京大学 | Method of manufacturing two-dimension periodic semi-sphere shell dot matrix of large scale zinc oxide |
| KR20110132893A (en) * | 2010-06-03 | 2011-12-09 | 이화여자대학교 산학협력단 | Carbon nanostructures loaded with metal nanoparticles, fabrication method thereof and application for electrode materials in fuel cells |
| CN104399480A (en) * | 2014-11-25 | 2015-03-11 | 天津工业大学 | Preparation and application of perovskite catalyst with three-dimensional ordered macroporous structure |
| CN104817280A (en) * | 2015-04-22 | 2015-08-05 | 陕西科技大学 | Preparation method of red photonic crystal structure color thin film with photo-catalytic effect |
| CN107681163A (en) * | 2017-09-21 | 2018-02-09 | 上海交通大学 | A kind of fuel cell membrane electrode and its preparation method and application |
| CN109860633A (en) * | 2019-02-13 | 2019-06-07 | 苏州擎动动力科技有限公司 | The preparation method and purposes of a kind of order mesoporous Catalytic Layer and membrane electrode |
| CN113659160A (en) * | 2021-08-17 | 2021-11-16 | 中汽创智科技有限公司 | Preparation method of mesoporous carbon supported nano platinum catalyst |
-
2021
- 2021-11-24 CN CN202111408415.9A patent/CN114122415A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101000967A (en) * | 2007-01-11 | 2007-07-18 | 上海交通大学 | Membrane electrode of protone exchange membrane fuel cell and preparation method thereof |
| CN101109070A (en) * | 2007-07-02 | 2008-01-23 | 南京大学 | Method of manufacturing two-dimension periodic semi-sphere shell dot matrix of large scale zinc oxide |
| KR20110132893A (en) * | 2010-06-03 | 2011-12-09 | 이화여자대학교 산학협력단 | Carbon nanostructures loaded with metal nanoparticles, fabrication method thereof and application for electrode materials in fuel cells |
| CN104399480A (en) * | 2014-11-25 | 2015-03-11 | 天津工业大学 | Preparation and application of perovskite catalyst with three-dimensional ordered macroporous structure |
| CN104817280A (en) * | 2015-04-22 | 2015-08-05 | 陕西科技大学 | Preparation method of red photonic crystal structure color thin film with photo-catalytic effect |
| CN107681163A (en) * | 2017-09-21 | 2018-02-09 | 上海交通大学 | A kind of fuel cell membrane electrode and its preparation method and application |
| CN109860633A (en) * | 2019-02-13 | 2019-06-07 | 苏州擎动动力科技有限公司 | The preparation method and purposes of a kind of order mesoporous Catalytic Layer and membrane electrode |
| CN113659160A (en) * | 2021-08-17 | 2021-11-16 | 中汽创智科技有限公司 | Preparation method of mesoporous carbon supported nano platinum catalyst |
Non-Patent Citations (2)
| Title |
|---|
| LIN DAI等: ""The fabrication of palladium hollow sphere array and application as highly active electrocatalysts for the direct oxidation of ethanol"", 《 ELECTROCHEMISTRY COMMUNICATIONS》, vol. 13, no. 12, pages 525 - 1528 * |
| 吴朵朵等: """聚苯乙烯微球自组装胶态晶体的研究及其应用进展""", 《功能材料》, vol. 47, no. 5, pages 05055 - 05067 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Du | Recent advances in electrode design based on one-dimensional nanostructure arrays for proton exchange membrane fuel cell applications | |
| US20100239952A1 (en) | Ionic electrolyte membrane structure, method for its production and solid oxide fuel cell making use of ionic electrolyte membrane structure | |
| CN108448138B (en) | Preparation method of fuel cell electrode and membrane electrode with full-ordered structure of catalyst layer | |
| CN110492109B (en) | Wide-width humidity self-adaptive fuel cell gas diffusion layer | |
| CN101752570B (en) | Preparation method of proton exchange membrane fuel cell electrode | |
| CN103199268A (en) | Ordered nanostructure membrane based on nanoimprint technology, and preparation and application of ordered nanostructure membrane electrode | |
| EP3709409A1 (en) | Microporous layer structure of fuel cell and preparation method therefor, and fuel cell cathode assembly | |
| CN102104155A (en) | Low-platinum cathode catalyst layer used for fuel cell and application thereof | |
| CN110400953A (en) | A kind of solid electrolyte water electrolysis membrane electrode and preparation method thereof | |
| CN101656315A (en) | Catalyst layers having thin film mesh catalyst (TFMC) and fuel cell electrode assembly | |
| CN102074715B (en) | Double-effect membrane electrode for integrated regenerative fuel cell and preparation method thereof | |
| Ding et al. | Electrochemically grown ultrathin platinum nanosheet electrodes with ultralow loadings for energy-saving and industrial-level hydrogen evolution | |
| CN101569039A (en) | Membrane-electrode assembly and fuel cell comprising the same | |
| CN114122415A (en) | Cathode structure catalyst layer of proton exchange membrane fuel cell and preparation method and application thereof | |
| CN103326032B (en) | Method for preparing platinum gradient-distribution catalyst layer structure of proton exchange membrane fuel cell | |
| CN103367768A (en) | Method for preparing double-catalyst-layer structure of proton exchange membrane fuel cell | |
| CN106299426B (en) | A kind of preparation process of membrane electrode | |
| Zhou et al. | Co9S8@ NiFe-LDH bifunctional electrocatalysts as high-efficiency cathodes for Zn–air batteries | |
| CN113161590A (en) | Preparation method and application of membrane electrode with self-supporting ordered structure | |
| CN102544529A (en) | Thin film catalyst on porous media and electrochemical cell employing same | |
| CN104795579A (en) | Single SOFC (solid oxide fuel cell) provided with cathode current collection layer and manufacturing method of single SOFC | |
| CN109772179B (en) | Method for preparing film by utilizing electrodeposition cobalt hydroxide nanosheet | |
| CN103474683A (en) | Membrane electrode assembly for improving performance of integrated regenerative fuel cell and preparation method of membrane electrode assembly | |
| CN106033817B (en) | Amberplex, preparation method and the application of nano array structure | |
| CN114628694A (en) | Preparation method and application of membrane electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |